Composition comprising polymers having a star structure, the polymers, and their use

ABSTRACT

A composition, comprising, in a physiologically acceptable medium, at least one polymer with a highly specific ordered structure is disclosed. These compositions find a specific application in the field of caring for or making up keratinous fibers, in particular as a mascara composition for the eyelashes or for the hair.

This is a continuation of application Ser. No. 09/543,935, filed Apr. 5,2000 now U.S. Pat. No. 6,476,124 which is incorporated herein byreference.

The present invention relates to a composition, in particular a cosmeticcomposition, comprising, in a physiologically acceptable medium, atleast one polymer with a highly specific ordered structure. Thesecompositions find a specific application in the field of caring for ormaking up keratinous fibres, in particular as a mascara composition forthe eyelashes or for the hair.

It is common practice to produce mascara compositions comprising atleast one wax. However, the wax is never used alone because make-up withsuch compositions proves to be very mediocre, leading to the formation,on the eyelashes, of a non-homogeneous film which is reflected by theformation of thin films which crack immediately after drying.

It is also known, for example according to Applications WO 96/36323 andWO 96/33690, to combine a wax and a film-forming polymer in a mascaracomposition. However, such a combination does not make it possible togive good curling to the eyelashes or to obtain a thick make-up on theeyelashes.

Mascara compositions comprising microdispersions of waxes in combinationwith film-forming polymers have also been provided, for example inApplications EP-A-557,196 and EP-A-639,371. However, such compositionsdo not make it possible to obtain a thick make-up on the eyelashes,these mascaras not having a high load.

The Inventor has found that, surprisingly and unexpectedly, the use ofhighly specific polymers exhibiting a specific ordered structure canmake it possible to obtain a composition capable of being applied tokeratinous fibres, in particular the eyelashes, which can make possibleimproved curling of the eyelashes, the curling furthermore beinginstantaneous and long-lasting.

Thus, a subject-matter of the present invention is a polymer with a“star” structure represented by the following formula (I):

A-[(M1)_(p1)-(M2)_(p2) . . . (Mi)_(pj)]_(n)

in which:

A represents a polyfunctional centre, with a functionality of “n”, nbeing an integer greater than or equal to 2,

[(M1)_(p1)-(M2)_(p2) . . . (Mi)_(pj)] represents a polymer chain, alsoknown as a “branch”, composed of identical or different polymerizedmonomers Mi having a polymerization index pj, each branch beingidentical or different and being grafted covalently to the centre A;

i being greater than or equal to 1 and pj being greater than or equal to2;

the polymer comprising one or more monomers Mi chosen from polymerizedmonomeric units Mk, which may be identical or different, wherein ahomopolymer formed by the corresponding polymerized monomers Mk has a Tgof greater than or equal to approximately 10° C., preferably of greaterthan or equal to 15° C. and even better still of greater than or equalto 20° C.

In a preferred embodiment, this or these monomers Mi being present, inthe final polymer, in a minimum amount of approximately 45% by weight,preferably in an amount of between 55 and 99% by weight and even betterstill in an amount of 75-95% by weight with respect to the total weightof monomers.

Another subject-matter of the present invention is a polymer asdescribed above further comprising one or more monomers Mj, thecorresponding homopolymer of which exhibits a Tg of less than or equalto approximately 10° C., preferably of less than or equal to 5° C. andeven better still of less than or equal to 0° C.

In a preferred embodiment, this or these monomers Mj are present in thefinal polymer in a maximum amount of approximately 55% by weight,preferably in an amount of between 1 and 45% by weight and even betterstill in an amount of 5-25% by weight with respect to the total weightof monomers.

Another subject-matter of the invention is a composition comprising, ina physiologically acceptable medium, at least one polymer as definedabove.

Another subject-matter of the invention is a process for the cosmetictreatment of keratinous fibres, in particular the eyelashes and/or hair,characterized in that it comprises applying, to the latter, a cosmeticcomposition as defined above.

Another subject-matter of the invention is the use of at least onepolymer as defined above in a cosmetic composition to be applied to theeyelashes, for allowing improved curling of the eyelashes to beobtained.

The compositions according to the invention exhibit a light texture andare very comfortable to wear throughout the day. They adhere well to thesubstrate to which they are applied.

They exhibit good resistance to water and can be easily removed, forexample using a conventional make-up remover, in particular one with anoily base.

The composition according to the invention therefore comprises apolymer, the “star” structure of which can be illustrated, in a generalway, by the following formula (I):

A-[(M1)_(p1)-(M2)_(p2) . . . (Mi)_(pj)]_(n)

in which:

A represents a polyfunctional centre, with a functionality of “n”, nbeing an integer greater than or equal to 2, preferably of between 4 and10,

[(M1)_(p1)-(M2)_(p2) . . . (Mi)_(pj)] represents a polymeric chain, alsoknown as a “branch”, composed of identical or different polymerizedmonomers Mi having a polymerization index pj, each branch beingidentical or different and being grafted covalently to the centre A;

i being greater than or equal to 1, preferably of between 2 and 10;

pj being greater than or equal to 2, preferably of between 10 and20,000.

The polymer chains are preferably provided in the form of blocks with amolecular mass of greater than or equal to 500 which can range up to2,000,000.

In a preferred embodiment, the polymer used in the context of thepresent invention can be obtained by controlled radical polymerization,also known as “living” radical polymerization. This technique makes itpossible in particular to overcome the limitations inherent inconventional radical polymerization, that is to say that it makes itpossible in particular to control the length of the chains of thepolymer which is formed and therefore to obtain block structures.

The controlled radical polymerization makes it possible to reduce thereactions in which the growing radical species is deactivated, inparticular the termination stage, which reactions, in conventionalradical polymerization, interrupt the growth of the polymer chain in anirreversible and uncontrolled way.

In order to decrease the probability of termination reactions, provisionhas been made to block, in a temporary and reversible way, the growingradical species by forming so-called “dormant” active species with theaid of a bond of low dissociation energy.

In particular, mention may be made of the possibility of using bonds ofC—ONR type (by reaction with a nitroxyl); this is illustrated inparticular by the article “Synthesis of nitroxy-functionalizedpolybutadiene by anionic polymerization using a nitroxy-functionalizedterminator”, published in Macromolecules, 1997, volume 30, pp.4238-4242.

Mention may also be made of the possibility of using bonds of C-halidetype (in the presence of metal/ligand complex). This is then describedas atom transfer radical polymerization, also known under theabbreviation ATRP. This type of polymerization is reflected in controlof the mass of the polymers which are formed and in a low polydispersityindex by weight of the chains.

Atom transfer radical polymerization is generally carried out bypolymerization:

of one or more radically polymerizable monomers, in the presence

of an initiator having at least one radically transferable atom orgroup,

of a compound comprising a transition metal capable of participating ina reduction stage with the initiator and a “dormant” polymer chain, and

of a ligand, which can be chosen from compounds comprising a nitrogen(N), oxygen (O), phosphorus (P) or sulphur (S) atom, which compounds arecapable of coordinating via a σ bond to the compound comprising atransition metal, or from compounds comprising a carbon atom, whichcompounds are capable of coordinating via a π or σ bond to the compoundcomprising a transition metal, the formation of direct bonds between thecompound comprising a transition metal and the polymer in the course offormation being avoided.

This process is illustrated in particular in Application WO97/18247, theteaching of which can be drawn upon by a person skilled in the art inpreparing the polymers coming within the scope of the present invention.

The nature and the amount of the monomers, initiator(s), compound(s)comprising the transition metal and ligand(s) will be chosen by a personskilled in the art on the basis of his overall knowledge, according tothe result desired.

In particular, the monomers “M” (Mi, Mk, and Mj) can be chosen, alone oras a mixture, from radically polymerizable compounds comprisingethylenic unsaturation corresponding to the formula:

in which R₁, R₂, R₃ and R₄ are, independently of one another, chosenfrom:

a hydrogen atom;

a halogen atom;

a linear or branched alkyl radical having 1 to 20, preferably 1-6, morepreferably 1-4, carbon atoms which is optionally substituted by one ormore halogens and/or one or more —OH radicals;

a linear or branched alkenyl or alkynyl radical having 2 to 10,preferably 2-6, more preferably 2-4, carbon atoms which is optionallysubstituted by one or more halogens;

a cyclic hydrocarbonaceous (cycloalkyl) radical having 3 to 8 carbonatoms which is optionally substituted by one or more halogen, nitrogen,sulphur or oxygen atoms;

a radical chosen from CN, C(═Y)R⁵, C(═Y)NR⁶R⁷, YC(═Y)R⁵, cyclicNC(═Y)R⁵, SOR⁵, SO₂R⁵, OSO₂R⁵, NR⁸SO₂R⁵, PR⁵ ₂, P(═Y)R⁵ ₂, YPR⁵ ₂,YP(═Y)R⁵ ₂, NR⁸ ₂, which can be quaternized with an additional R⁸ group,aryl and heterocyclyl, with:

Y represents O, S or NR⁸ (preferably O),

R⁵ represents a linear or branched alkyl, alkylthio or alkoxy radicalhaving 1-20 carbon atoms; an OH radical; an OM′ radical with M′=alkalimetal; an aryloxy radical or a heterocyclyloxy radical;

R⁶ and R⁷ represent, independently of one another, H or a linear orbranched alkyl radical having 1-20 carbon atoms; it being given that R⁶and R⁷ can be joined to form an alkylene group having 2-7, preferably2-5, carbon atoms;

R⁸ represents H, a linear or branched alkyl radical having 1-20 carbonatoms or an aryl radical;

a —COOR radical, in which R is a linear or branched alkyl radical having1 to 20, preferably 1-6, carbon atoms which is optionally substituted byone or more halogens;

a —CONHR′ radical, in which R′ is hydrogen or a saturated orunsaturated, linear or branched, hydrocarbonaceous radical having 1 to20, preferably 1-6, carbon atoms which is optionally substituted by oneor more halogens, nitrogens and/or oxygens;

an —OCOR″ radical, in which R″ is hydrogen or a saturated orunsaturated, linear or branched, hydrocarbonaceous radical having 1 to20 carbon atoms which is optionally substituted by one or more halogens,nitrogens and/or oxygens;

a radical comprising at least one silicon atom and in particularradicals such as: an —R-siloxane radical, a —CONHR-siloxane radical, a—COOR-siloxane radical or an —OCO—R-siloxane radical, in which radicalsR is a linear or branched alkyl, alkylthio, alkoxy, aryloxy orheterocycloxy radical having 1-20 carbon atoms.

The term “siloxane” is understood to mean a compound comprising(—SiR^(a)R^(b)O—)_(n) units, in which units R^(a) and R^(b) canrepresent, independently of one another, a hydrogen; a halogen; asaturated or unsaturated, linear or branched, hydrocarbonaceous radicalhaving 1 to 36 carbon atoms which is optionally substituted by one ormore halogens, nitrogens and/or oxygens; or a cyclic hydrocarbonaceousradical having 1 to 20 carbon atoms; n being greater than or equal to 1.

For the purpose of this invention, the term “independent,” when used todescribe the relationship of radicals, atoms, substituents, functionalgroups, etc., means that each of the radicals, atoms, substituents,functional groups, etc. may be the same or different from the other, orsome radicals, atoms, substituents functional groups, etc., may be thesame while the others may be different.

Mention may in particular be made of polydimethylsiloxanes (PDMSs)comprising 1 to 200, preferably less than 100, repeat units.

Furthermore, R¹ and R³ can be connected to one another so as to form aring of formula (CH₂)_(n) which can be substituted by one or morehalogens and/or oxygens and/or nitrogens and/or by alkyl radicals having1 to 6 carbon atoms.

The term “aryl” or “heterocyclyl” is understood to mean the definitioncommonly understood by a person skilled in the art and which may beillustrated by the prior art WO97/18247.

Preferably, the monomers M can be chosen from:

acrylic or methacrylic esters obtained from linear, branched or cyclicaliphatic alcohols and/or from aromatic alcohols, preferably C₁-C₂₀alcohols, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl(meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate ortert-butyl (meth)acrylate;

C₁-C₄ hydroxyalkyl (meth)acrylates, such as 2-hydroxyethyl(meth)acrylate or 2-hydroxypropyl (meth)acrylate;

ethylene glycol, diethylene glycol or polyethylene glycol(meth)acrylates with a hydroxyl or ether end;

vinyl, allyl or methallyl esters obtained from linear or branched C₁-C₁₀or cyclic C₁-C₆ aliphatic alcohols and/or from aromatic alcohols,preferably C₁-C₆ alcohols, such as vinyl acetate, vinyl propionate,vinyl benzoate or vinyl tert-butylbenzoate;

N-vinylpyrrolidone; vinylcaprolactam; vinyl-N-alkylpyrroles having 1 to6 carbon atoms; vinyloxazoles; vinylthiazoles; vinylpyrimidines;vinylimidazoles; and vinyl ketones;

(meth)acrylamides obtained from linear, branched or cyclic aliphaticamines and/or from aromatic amines, preferably C₁-C₂₀ amines, such astert-butylacrylamide; and (meth)acrylamides, such as acrylamide,methacrylamide or di(C₁-C₄)alkyl(meth)acrylamides;

olefins, such as ethylene, propylene, styrene or substituted styrene;

fluorinated or perfluorinated acrylic or vinyl monomers, in particular(meth)acrylic esters with perfluoroalkyl units;

monomers comprising an amine functional group in the free or elsepartially or completely neutralized or else partially or completelyquaternized form, such as dimethylaminoethyl (meth)acrylate,dimethylaminoethylmethacrylamide, vinylamine, vinylpyridine ordiallyldimethylammonium chloride;

carboxybetaines or sulphobetaines obtained by partial or completequaternization of monomers comprising ethylenic unsaturation comprisingan amine functional group by sodium salts of carboxylic acids comprisinga mobile halide (sodium chloroacetate, for example) or by cyclicsulphones (propane sulphone);

silicone-comprising (meth)acrylates or (meth)acrylamides, in particular(meth)acrylic esters comprising siloxane units;

their mixtures.

The particularly preferred monomers are chosen from:

(meth)acrylic esters obtained from linear or branched aliphaticalcohols, preferably C₁-C₂₀ alcohols;

C₁-C₂₀ (meth)acrylic esters comprising perfluoroalkyl units;

C₁-C₂₀ (meth)acrylic esters comprising siloxane units;

(meth)acrylamides obtained from linear, branched or cyclic aliphaticamines and/or from aromatic amines, preferably C₁-C₂₀ amines, such astert-butylacrylamide; or (meth)acrylamides, such as acrylamide,methacrylamide or di(C₁-C₄)alkyl(meth)acrylamides;

vinyl, allyl or methallyl esters obtained from linear or branched C₁-C₁₀or cyclic C₁-C₆ aliphatic alcohols;

vinylcaprolactam;

optionally substituted styrene;

their mixtures.

In the context of the present invention, the initiator can be anycompound, in particular a molecular or polymeric compound, having atleast two atoms and/or groups which are radically transferable bypolymerization.

The initiator can in particular be an oligomer or a polymer capable ofbeing obtained by radical polymerization, by polycondensation, byanionic or cationic polymerization or by ring opening.

The transferable atoms and/or groups can be situated at the ends of thepolymer chain or along the backbone.

Mention may in particular be made of the compounds corresponding to oneof the following formulae:

R¹¹CO—X

R¹¹ _(x)R¹² _(y)R¹³ _(z)C—(RX)_(t), in which x, y and z represent aninteger ranging from 0 to 4, t an integer ranging from 1 to 4, andx+y+z=4−t;

R¹³ _(x)C₆—(RX)_(y) (saturated ring with 6 carbons), in which xrepresents an integer ranging from 7 to 11, y represents an integerranging from 1 to 5, and x+y=12;

R¹³ _(x)C₆—(RX)_(y) (unsaturated ring with 6 carbons), in which xrepresents an integer ranging from 0 to 5, y represents an integerranging from 1 to 6, and x+y=6;

—[—(R¹¹)(R¹²)(R¹³)C—(RX)—]_(n), in which n is greater than or equal to1; cyclic or linear;

—[—(R¹²)_(x)C₆(RX)_(y)—R¹¹—]_(n), in which x represents an integerranging from 0 to 6, y represents an integer ranging from 1 to 6 and nis greater than or equal to 1, with x+y=4 or 6; cyclic or linear;

—[—(R¹²)_(x)C₆(RX)_(y)—R¹¹—]_(n), in which x represents an integerranging from 0 to 12, y represents an integer ranging from 1 to 12 and nis greater than or equal to 1, with x+y=10 or 12; cyclic or linear;

R¹¹R¹²R¹³Si—X

—[OSi(R¹¹)_(x)(RX)_(y)]_(n), cyclic or linear, in which x and yrepresent an integer ranging from 0 to 2 and n is greater than or equalto 1, with x+y=2;

R¹¹R¹²N—X

R¹¹N—X₂

(R¹¹)_(x)P(O)_(y)—X_(3−x) in which x and y represent integers rangingfrom 0 to 2 and x+y=5;

(R¹¹O)_(x)P(O)_(y)—X_(3−x) in which x and y represent integers rangingfrom 0 to 2 and x+y=5;

—[(R¹¹)_(t)N_(z)P(O)_(x)(O—RX)_(y)—]_(n), cyclic or linear, in which xrepresents an integer ranging from 0 to 4, y represents an integerranging from 1 to 5, z represents an integer ranging from 0 to 2, trepresents an integer ranging from 0 to 3 and n is greater than or equalto 1;

in which:

R, R¹¹, R¹² and R¹³ represent, independently of one another, a hydrogenor halogen atom; a linear or branched alkyl radical having 1-20,preferably 1-10 and more preferably 1-6 carbon atoms; a cycloalkylradical having 3-8 carbon atoms; a —C(═Y)R⁵, —C(═Y)NR⁶R⁷ or —R⁸ ₃Siradical (see the definitions of R⁵ to R⁸ above); —COCl; —OH; —CN; analkenyl or alkynyl radical having 2-20, preferably 2-6, carbon atoms; anoxiranyl or glycidyl radical or an alkylene or alkenylene radicalsubstituted with an oxiranyl or a glycidyl; an aryl, heterocyclyl,aralkyl or aralkenyl radical; or an alkyl radical having 1-6 carbonatoms in which all or part of the hydrogen atoms are substituted eitherby halogen atoms, such as fluorine, chlorine or bromine, or by an alkoxygroup having 14 carbon atoms or by an aryl, heterocyclyl, —C(═Y)R⁵,—C(═Y)NR⁶R⁷, oxiranyl or glycidyl radical;

X represents a halogen atom, such as Cl, Br or I, or an —OR′, —SR, —SeR,—OC(═O)R′, —OP(═O)R′, —OP(═O)(OR′)₂, —OP(═O)OR′, —O—NR′₂, —S—C(═S)NR′₂,—CN, —NC, —SCN, —CNS, —OCN, —CNO and —N₃ radical, in which R′ representsan alkyl radical having 1-20 carbon atoms which is optionallysubstituted by one or more halogen atoms, in particular fluorine and/orchlorine atoms, and R represents a linear or branched alkyl or arylradical having 1-20, preferably 1-10, carbon atoms, it additionallybeing possible for the —NR′₂ group to represent a cyclic group, the twoR′ groups being joined so as to form a 5-, 6- or 7-membered heterocycle.

Preferably, X represents a halogen atom and in particular a chlorine orbromine atom.

The initiator is preferably chosen from the compounds of formula

R¹³ _(x)C₆—(RX)_(y) (saturated ring with 6 carbons) in which xrepresents an integer ranging from 7 to 11, y represents an integerranging from 1 to 5 and x+y=12;

—[—(R¹²)_(x)C₆(RX)_(y)—R¹¹—]_(n), in which x represent an integerranging from 0 to 6, y represents an integer ranging from 1 to 6 and nis greater than or equal to 1, with x+y=4 or 6; cyclic or linear; and

—[OSi(R¹¹)_(x)(RX)_(y)]_(n), cyclic or linear, in which x and yrepresent an integer ranging from 0 to 2 and n is greater than or equalto 1, with x+y=2.

Mention may in particular be made, as initiator, of the followingcompounds:

octa(2-isobutyrylbromide)octa(tert-butyl)calix(8)arene,

octa(2-propionylbromide)octa(tert-butyl)calix(8)arene, and

hexakis(α-bromomethyl)benzene.

The compound comprising a transition metal which is capable ofparticipating in a reduction stage with the initiator and a “dormant”polymer chain can be chosen from those which correspond to the formulaM^(n+)X′_(n), in which formula:

M can be chosen from Cu, Au, Ag, Hg, Ni, Pd, Pt, Rh, Co, Ir, Fe, Ru, Os,Re, Mn, Cr, Mo, W, V, Nb, Ta and Zn,

X′ can represent a halogen (in particular bromine or chlorine), OH,(O)_(½), an alkoxy radical having 1-6 carbon atoms, (SO₄)_(½),(PO₄)_(⅓), (HPO₄)_(½), (H₂PO₄), a triflate, hexafluorophosphate,methanesulphonate, arylsulphonate, SeR, CN, NC, SCN, CNS, OCN, CNO, N₃and R′CO₂ radical, in which R represents a linear or branched alkyl oraryl radical having 1-20, preferably 1-10, carbon atoms and R′represents H or a linear or branched alkyl radical having 1-6 carbonatoms or an aryl radical which is optionally substituted by one or morehalogen atoms, in particular fluorine and/or chlorine atoms;

n is the charge on the metal.

The choice is preferably made of M representing copper or ruthenium andX′ representing bromine or chlorine.

Mention may in particular be made of copper bromide.

Mention may be made, among the ligands capable of being used in thecontext of the present invention, of compounds comprising at least onenitrogen, oxygen, phosphorus and/or sulphur atom which are capable ofcoordinating via a σ bond to the compound comprising a transition metal.

Mention may also be made of compounds comprising at least two carbonatoms which are capable of coordinating via a π bond to the compoundcomprising a transition metal.

Mention may further be made of compounds comprising at least one carbonatom which are capable of coordinating via a σ bond to the compoundcomprising a transition metal but which do not form a carbon—carbon bondwith the monomer during the polymerization, that is to say which do notparticipate in β-addition reactions with the monomers.

Mention may further be made of compounds capable of coordinating via μor η bond to the compound comprising a transition metal.

Mention may in particular be made of the compounds of formula:

R⁹—Z—(R¹⁴—Z)_(m)—R¹⁰

in which:

R⁹ and R¹⁰ are, independently of one another, a hydrogen atom; a linearor branched alkyl radical having 1-20, preferably 1-10, carbon atoms; anaryl radical; a heterocyclyl radical; or an alkyl radical having 1-6carbon atoms which is substituted with an alkoxy radical having 1-6carbon atoms or a dialkylamino radical having 14 carbon atoms or a—C(═Y)R⁵ or —C(═Y)NR⁶R⁷ and/or YC(═Y)R⁸ radical (see the definitions R⁵to R⁸ and Y above); it being given that R⁹ and R¹⁰ can be joined so asto form a saturated or unsaturated ring;

R¹⁴ represents, independently of one another, a divalent group chosenfrom alkanediyls having 24 carbon atoms; alkenylenes having 24 carbonatoms; cycloalkanediyls having 3-8 carbon atoms; cycloalkenediyls having3-8 carbon atoms; arenediyls and heterocyclylenes;

Z represents O, S, NR¹⁵ or PR¹⁵, with R¹⁵ representing H; a linear orbranched alkyl radical having 1-20 carbon atoms; an aryl radical; aheterocyclyl radical; or an alkyl radical having 1-6 carbon atoms whichis substituted with an alkoxy radical having 1-6 carbon atoms or adialkylamino radical having 14 carbon atoms or a —C(═Y)R⁵ or —C(═Y)NR⁶R⁷and/or YC(═Y)R⁸ radical (see the definitions of R⁵ to R⁸ and Y above);

m is between 0 and 6.

Mention may also be made of the compounds of formula:

R²⁰R²¹C[C(═Y)R⁵]

in which:

R²⁰ and R²¹ are, independently of one another, a hydrogen atom; ahalogen atom; a linear or branched alkyl radical having 1-20, preferably1-10, carbon atoms; an aryl radical; or a heterocyclyl radical; it beinggiven that R²⁰ and R²¹ can be joined so as to form a saturated orunsaturated ring; it being given that, in addition, each radical can besubstituted with an alkyl radical having 1-6 carbon atoms, an alkoxyradical having 1-6 carbon atoms or an aryl radical;

R⁵ and Y being defined above.

Mention may further be made, as ligands, of carbon monoxide; optionallysubstituted porphyrins and porphycenes; optionally substitutedethylenediamine and propylenediamine; polyamines with tertiary amines,such as pentamethyldiethylenetriamine; aminoalcohols, such asaminoethanol and aminopropanol, which are optionally substituted;glycols, such as ethylene glycol or propylene glycol, which areoptionally substituted; arenes, such as benzene, which are optionallysubstituted; optionally substituted cyclopentadiene; optionallysubstituted pyridines and bipyridines; acetonitrile;1,10-phenanthroline; cryptands and crown ethers; or sparteine.

The preferred ligands are chosen in particular from pyridines andbipyridines which are optionally substituted by C₂-C₁₅ alkyl radicals,in particular C₆-C₁₂ radicals and especially the nonyl radical; orpolyamines with tertiary amines, such as pentamethyldiethylenetriamine.

The polymerization of the monomers, in the presence of the initiator, ofthe compound comprising a transition metal and of the ligand which actsas activator, results in the production of a polymer having a starstructure, which can be represented by the formula (I) given above, inwhich the monomers have polymerized to give “n” alike or differentpolymer chains all connected to a polyfunctional centre A which derivesfrom the initiator.

It has been found that, in order to achieve the goal pursued by thepresent invention, that is to say to obtain a composition which does notexhibit the disadvantages of the prior art and which in particularallows sufficient curling of the eyelashes to be obtained, it ispreferable to choose a polymer corresponding to the following criteria:

it preferably comprises one or more monomers Mi, the correspondinghomopolymer of which exhibits a Tg of greater than or equal toapproximately 10° C., preferably of greater than or equal to 15° C. andeven better still of greater than or equal to 20° C.;

this or these monomers Mi being present in the final polymer in aminimum amount of approximately 45% by weight, preferably in an amountof between 55 and 99% by weight and even better still in an amount of75-95% by weight with respect to the total weight of monomers.

The polymer may or may not comprise other monomers.

However, it is possible for it to additionally comprise one or moremonomers Mj, the corresponding homopolymer of which exhibits a Tg ofless than or equal to approximately 10° C., preferably of less than orequal to 5° C. and even better still of less than or equal to 0° C.

In this case, this or these monomers Mj are present in the final polymerin a maximum amount of approximately 55% by weight, preferably in anamount of between 1 and 45% by weight and even better still in an amountof 5-25% by weight with respect to the total weight of monomers.

The Tg (glass transition temperature) is measured by DSC (DifferentialScanning Calorimetry) according to ASTM Standard D3418-97.

The polymers as defined in the present invention are preferably befilm-forming or can be rendered film-forming by addition of anadditional agent which is able to form a film. The term “film-forming”is understood to mean that the polymer, after application to a substrateand evaporation of the solvent (aqueous or organic), results in atransparent and uncracked film.

Such an additional agent which is able to form a film can be chosen fromany compound known to a person skilled in the art as being capable offulfilling the desired role and can be chosen in particular fromplasticizing agents and/or from coalescence agents. Mention may inparticular be made, alone or as a mixture, of:

glycols and their derivatives, such as diethylene glycol ethyl ether,diethylene glycol methyl ether, diethylene glycol butyl ether,diethylene glycol hexyl ether, ethylene glycol ethyl ether, ethyleneglycol butyl ether or ethylene glycol hexyl ether;

glycerol esters, such as glycerol diacetate (diacetin) and glyceroltriacetate (triacetin);

propylene glycol derivatives, in particular propylene glycol phenylether, propylene glycol diacetate, propylene glycol methyl ether,propylene glycol ethyl ether, propylene glycol butyl ether, dipropyleneglycol methyl ether, dipropylene glycol butyl ether, dipropylene glycolethyl ether, tripropylene glycol butyl ether or tripropylene glycolmethyl ether;

acid esters, in particular carboxylic acid esters, such as citrates,phthalates, adipates, carbonates, tartrates, phosphates or sebacates,

oxyethylenated derivatives, such as oxyethylenated oils, in particularvegetable oils, such as castor oil; or oxyethylenated silicone oils.

The amount of additional agent which is able to form a film can bechosen by a person skilled in the art on the basis of his overallknowledge so as to form a film having the desired mechanical propertieswhile retaining, in the composition, cosmetically acceptable properties.

In a preferred embodiment of the invention, a polymer, optionally incombination with additional agents which are able to form a film, ischosen which makes it possible to obtain a film having the followingphysicochemical characteristic:

a retraction of the isolated stratum corneum which is greater thanapproximately 1%, preferably greater than or equal to 1.1%, measuredusing a dermometer, at 30° C., under a relative humidity of 40%, for aconcentration of 7% of polymer in a solvent such as isododecane orwater.

The polymers as defined above can be present in the medium in a formdissolved or dispersed in an aqueous, organic or aqueous/organic phase,in particular an alcoholic or aqueous/alcoholic phase.

The polymers can be present in the composition according to theinvention in an amount which can be easily determined by a personskilled in the art according to the application envisaged and which canbe between 1-99% by weight, on a dry basis, with respect to the totalweight of the composition, preferably between 1.5-50% by weight andpreferably between 2-30% by weight.

The compositions, in particular cosmetic compositions, according to the,invention therefore additionally comprise a physiologically acceptablemedium which can be chosen by a person skilled in the art according tothe application envisaged.

This medium can comprise an aqueous phase and/or a fatty phase. It canalso be anhydrous.

The aqueous phase can comprise water and/or a thermal water and/or aspring water and/or a mineral water and/or a floral water.

It can also comprise one or more cosmetically acceptable organicsolvents or else a mixture of water and of one or more cosmeticallyacceptable organic solvents. Mention may be made, among these organicsolvents, of:

C₁-C₄ alcohols, such as ethanol, ispropanol or n-propanol;

ethers, such as dimethoxyethane;

ketones, such as acetone or methyl ethyl ketone;

lower C₁-C₃ carboxylic acid esters, such as methyl acetate or ethylacetate.

The fatty phase can comprise conventional volatile or non-volatile oils,gums and/or waxes of animal, vegetable, mineral or synthetic origin,alone or as mixtures, in particular:

linear, branched or cyclic, volatile or non-volatile, silicone oilswhich are optionally organomodified; phenylated silicones; or siliconeresins and gums which are liquid at room temperature;

mineral oils, such as liquid paraffin and liquid petrolatum;

oils of animal origin, such as perhydrosqualene or lanolin;

oils of vegetable origin, such as liquid triglycerides, for examplesunflower, maize, soybean, jojoba, gourd, grape seed, sesame, hazlenut,apricot, macadamia, avocado, sweet almond or castor oils, triglyceridesof caprylic/capric acids, olive oil, groundnut oil, rapeseed oil orcoconut oil;

synthetic oils, such as purcellin oil, isoparaffins, fatty alcohols oresters of fatty acids;

fluorinated and perfluorinated oils or fluorinated silicone oils;

waxes chosen from known animal, fossil, vegetable, mineral or syntheticwaxes, such as paraffin waxes, polyethylene waxes, carnauba orcandelilla waxes, beeswaxes, lanolin wax, chinese insect waxes, ricewax, ouricury wax, esparto wax, cork fibre wax, sugarcane wax, japanwax, sumach wax, montan wax, microcrystalline waxes, ozokerite, thewaxes obtained by the Fischer-Tropsch synthesis, silicone waxes or theirmixtures.

The composition can additionally comprise at least one water-soluble dyeand/or at least one pigment which are used conventionally in the fieldof cosmetics and make-up. The term “pigments” should be understood asmeaning white or coloured and inorganic or organic particles which areinsoluble in the medium and which are intended to colour and/or opacifythe composition. The pigments can be present in the composition in aproportion of 0-20% by weight of the final composition and preferably ina proportion of 1-5%. They can be white or coloured, inorganic and/ororganic and conventional or nanometric in size. Mention may be made,among inorganic pigments and nanopigments, of titanium, zirconium orcerium oxides, as well as zinc, iron or chromium oxides or ferric blue.Mention may be made, among organic pigments, of carbon black and barium,strontium, calcium or aluminium lakes. Mention may be made, amongwater-soluble dyes, of the dyes which are standard in the field underconsideration, such as the disodium salt of ponceau, the disodium saltof alizarine, quinoline yellow, the trisodium salt of amaranth, thedisodium salt of tartrazine, the monosodium salt of rhodamine, thedisodium salt of fuchsine or xanthophyll.

Furthermore, the composition according to the invention can compriseadjuvants commonly used in cosmetic or pharmaceutical compositionsintended in particular for a topical application. In particular, thesecompositions can comprise:

cosmetic and/or pharmaceutical active principles, such as softeners,antioxidants, opacifiers, emollients, hydroxy acids, antifoaming agents,moisturizers, vitamins, fragrances, preservatives, sequestering agents,UV screening agents, ceramides, agents for combating free radicals,bactericides, antidandruff agents, complexing agents, agents forcombating hair loss, or antifungal or antiseptic agents;

fillers, pearlescent agents, lakes, thickeners, gelling agents,polymers, in particular fixing or conditioning polymers, propellants,basifying or acidifying agents, or plasticizers;

additional hydrophilic polymers, such as poly(vinyl alcohol)s and theircopolymers, polysaccharides or cellulose polymers, or natural proteinsor synthetic polypeptides;

film-forming polymers, in particular in aqueous dispersion;

surfactants, in particular anionic or non-ionic surfactants, which areoptionally silicone surfactants.

Of course, a person skilled in the art will take care to choose this orthese optional adjuvants and/or their amounts so that the advantageousproperties of the composition according to the invention are not, or notsubstantially, detrimentally affected by the envisaged addition.

The compositions according to the invention can be provided in variousforms and in particular in the form of oil-in-water, water-in-oil ormultiple emulsions; of aqueous or oily dispersions or of dispersions ina solvent medium; of aqueous, aqueous/alcoholic or oily solutions or ofsolutions in a solvent medium; of aqueous or oily gels; or ofmicroemulsions.

The compositions according to the invention find an application inparticular as cosmetic compositions for caring for or making upkeratinous fibres, in particular eyelashes and/or hair.

The invention is illustrated in more detail in the following examples.

A/Retraction Measurement Method

The principle includes measuring, before treatment and after treatment,the length of a test specimen of isolated stratum corneum and indetermining the percentage of retraction of the test specimen.

Use is made of 1 cm×0.4 cm test specimens of stratum corneum with athickness ranging from 10 to 20 μm positioned on an MTT 6.0 extensometersold by the company Diastron.

The test specimen is placed between 2 jaws and then left for 12 hours inan atmosphere at 30° C. and 40% relative humidity.

The test specimen is tensioned at the rate of 2 mm/minute by a length ofbetween 5 and 10% of the initial length in order to determine the lengthL₁ from which the test specimen begins to exert a force on the jawsdetected by the device.

The test specimen is subsequently relaxed and then 2 mg of an aqueouscomposition comprising 7% by weight of polymer are applied to thestratum corneum. After complete evaporation of the composition, the testspecimen is tensioned under the same conditions as those described abovein order to also determine the length L₂ for the treated test specimen.

The percentage of retraction is determined by the ratio:

100×(L ₂ −L ₁)/L ₁.

EXAMPLE 1 Preparation of the Initiator

The initiator prepared was 5, 11, 17, 23, 29, 35, 41,47-octa(2-propionylbromide)-49, 50, 51, 52, 53, 54, 55,56-octa(tert-butyl)calix(8)arene (M=2378 g).

The reactants used were as follows:

4-(tert-butyl)calix(8)arene (M = 1298 g), comprising 8   15 g phenolunits (Aldrich) 2-bromopropionyl bromide of formula CH₃—CHBr—COBr 59.9 gtriethylamine   28 g tetrahydrofuran (THF)  120 g

The 4-(t-butyl)calix(8)arene and the solvent THF were added to around-bottomed flask equipped with a stirrer and a thermometer; themixture was left stirring for 10 minutes at room temperature.

The triethylamine was subsequently added, which took approximately 15minutes.

The 2-bromopropionyl bromide, dissolved beforehand in THF, was thenadded at a temperature of approximately 5° C., which took approximately1 h 30.

The mixture was left stirring for at least 12 hours at 5° C. and thenthe temperature was allowed to gradually rise to room temperature.

The solution obtained was concentrated by evaporating the THF. A productwas precipitated from a water/ice mixture, extraction was then carriedout with ethyl ether and the extract was dried over magnesium sulphate.

The solution obtained was concentrated and a compound was precipitatedfrom a methanol/ice (90/10) mixture in a compound/precipitant ratio of1/5.

23 g of compound were obtained, i.e., a yield of 85%, which compoundexisted in the form of a powder.

Characterization was carried out by NMR/GC or HPLC. The compoundobtained exhibited values in accordance with those expected.

EXAMPLE 2 Preparation of an 8-branched Star Polymer, Each Branch ofWhich was a Block Copolymer

1) First stage: preparation of a star polymer with 8 poly(isobutylmethacrylate) branches

The reactants used were as follows:

monomer 1: isobutyl methacrylate (Tg = 53° C.)  105 g monomer 2: butylacrylate (Tg = −50° C.)   15 g initiator (prepared according toExample 1) 1.19 g (corresponding to 4 × 10⁻³ mol of RBr) CuBr(corresponding to 4 × 10⁻³ mol) 0.57 g Bipyridine (corresponding to 8 ×10⁻³ mol) 1.25 g The monomers were distilled beforehand.

The reactants, except the monomers, were mixed in a sealed andflame-treated reactor comprising a nitrogen inlet and then the monomer 1was added.

The reactor was heated under nitrogen to approximately 120° C. andreaction was then allowed to take place at 120° C. for 4 hours, thenitrogen inlet being disconnected.

2) Second stage: formation of the second block at the end of each branch

The monomer 2 was then added and reaction was again allowed to takeplace at 120° C. for 4 hours.

After reaction, the reaction mixture was allowed to cool; a viscousgreen solution was obtained, which solution was dissolved indichloromethane. The polymer solution was passed through neutral aluminaand the clear solution obtained was precipitated from a methanol/water(80/20) mixture in a polymer/precipitant ratio of 1/5.

95 g of polymer were obtained, i.e., a yield of 95%, which polymerexisted in the form of a viscous product.

This polymer was a star polymer with 8 poly(isobutyl methacrylate)branches, each branch of which was a block copolymer:calix(poly(isobutyl methacrylate)-block-poly(butyl acrylate)).

Characterization was carried out by GC:THF linear polystyreneequivalent, light scattering detection: 304,000 g/mol (theoretical mass:approximately 240,000); polydispersity index: 1.38.

The polymer obtained exhibited values in accordance with those expected.

Retraction of the stratum corneum: 1.1%

EXAMPLE 3 Mascara

A waterproof mascara composition was prepared comprising:

paraffin wax 13 g lanolin alcohol 16 g iron oxides  5 g montmorillonite 9 g starch  2 g polymer obtained according to Example 2, 10 g of themixture as 20% by weight solution in isododecane Isoparaffin 45 g

A mascara was obtained which was easily applied and which made itpossible to obtain satisfactory curling of the eyelashes.

What is claimed is:
 1. A process for preparing a cosmetic composition,comprising introducing, in a cosmetically acceptable medium, at leastone polymer in an amount effective for curling keratinous fibers,wherein said at least one polymer having a star structure chosen fromstructures of formula (I): A-[(M1)_(p1)-(M2)_(p2) . . . (Mi)_(pj)]_(n)  (I) in which: A is chosen from polyfunctional centers having afunctionality n; [(M1)_(p1)-(M2)_(p2) . . . (Mi)_(pj)] represents abranch comprising at least one polymerized monomeric unit Mi having apolymerization index pj; n is an integer greater than or equal to 2; iis greater than or equal to 1; pj is greater than or equal to 2; the atleast two branches may be identical or different; and said at least twobranches are grafted covalently to A; and wherein said at least onepolymerized monomeric unit Mi comprised by at least one of said at leasttwo branches is chosen from polymerized monomeric units Mk, which may beidentical or different, wherein a homopolymer formed by thecorresponding polymerized monomeric units Mk has a Tg of greater than orequal to 10° C.
 2. A process according to claim 1, wherein said at leastone polymerized monomeric unit Mi chosen from polymerized monomericunits Mk is pressent in an amount greater than or equal to 45 percent byweight relative to the total weight of the polymerized monomeric unitsMi.
 3. A process according to claim 1, further comprising at least onepolymerized monomeric unit Mi contained by at least one of said at leasttwo branches chosen from polymerized monomeric units Mj, which may beidentical or different, wherein a homopolymer formed by thecorresponding polymerized monomeric units Mj has a Tg of less than orequal to 10° C.; and wherein said at least one polymerized monomericunit Mi chosen from polymerized monomeric units Mj is present in anamount less than or equal to 55 percent by weight relative to the totalweight of the polymerized monomeric units Mi.
 4. A process according toclaim 1, wherein said keratinous fibers are eyelashes.
 5. A polymeraccording to claim 1, wherein said homopolymer formed by thecorresponding polymerized monomeric units Mk has a Tg of greater than orequal to 15° C.
 6. A polymer according to claim 5, wherein said Tg has avalue of greater than or equal to 20° C.
 7. A polymer according to claim1, wherein said at least one polymerized monomeric unit Mi chosen frompolymerized monomers Mk is present in an amount ranging from 55 to 99percent by weight relative to the total weight of the polymerizedmonomeric units Mi.
 8. A polymer according to claim 7, wherein saidamount ranges from 75 to 95 percent.
 9. A polymer according to claim 3,wherein said homopolymer formed by the corresponding polymerizedmonomeric units Mj has a Tg of less than or equal to 5° C.
 10. A polymeraccording to claim 3, wherein said Tg has a value of less than or equalto 0° C.
 11. A polymer according to claim 3, wherein said at least onepolymerized monomeric unit Mi chosen from polymerized monomeric units Mjis present in an amount ranging from 1 to 45 percent by weight relativeto the total weight of the polymerized monomeric units Mi.
 12. A polymeraccording to claim 11, wherein said amount ranges from 5 to 25 percent.13. A polymer according to claim 1, wherein said at least one of saidbranches has a form of a block and a molecular mass ranging from 500 to2,000,000 Daltons.
 14. A polymer according to claim 1, wherein saidpolymerized monomeric unit Mk is chosen from radically polymerizablecompounds containing an ethylenic unsaturation having a formula:

in which: R₁, R₂, R₃, and R₄ are, each independently of one another,chosen from: a hydrogen atom; halogen atoms; linear and branched alkylradicals having from 1 to 20 carbon atoms which are optionallysubstituted by at least one halogen atom or at least one —OH radical;linear and branched alkenyl and alkynyl radicals having from 2 to 10carbon atoms which are optionally substituted by at least one halogenatom; cyclic hydrocarbonaceous radicals having from 3 to 8 carbon atomswhich are optionally substituted by at least one halogen atom, nitrogenatom, sulphur atom, or oxygen atom; radicals chosen from CN, C(═Y)R⁵,C(═Y)NR⁶R⁷, YC(═Y)R⁵, cyclic NC(═Y)R⁵, SOR⁵, SO₂R⁵, OSO₂R⁵, NR⁸SO₂R⁵,PR⁵ ₂, P(═Y)R⁵ ₂, YPR⁵ ₂, YP(═Y)R⁵ ₂, NR⁸ ₂, NR⁸ ₃ ⁺, NR⁸ ₂(aryl)⁺, andNR⁸ ₂(heterocycyl)⁺, in which: Y is chosen from O, S, and NR⁸; R⁵ ischosen from linear and branched alkyl radicals, alkylthio radicals, andalkoxy radicals having from 1 to 20 carbon atoms; an OH radical; OM′radicals in which M′ is chosen from alkali metals; aryloxy radicals; andheterocyclyloxy radical; R⁶ and R⁷, independently of one another, arechosen from a hydrogen atom, linear and branched alkyl radicals havingfrom 1 to 20 carbon atoms; or R⁶ and R⁷ together form an alkylene grouphaving from 2 to 7 carbon atoms; R⁸ is chosen from a hydrogen atom,linear and branched alkyl radicals having from 1 to 20 carbon atoms andan aryl radical; COOR radicals, in which R is chosen from linear andbranched alkyl radicals having from 1 to 20 carbon atoms which areoptionally substituted by at least one halogen atom; CONHR′ radicals, inwhich R′ is chosen from hydrogen atoms and saturated and unsaturated,linear and branched, hydrocarbonaceous radicals having from 1 to 20carbon atoms which are optionally substituted by at least one halogenatom, nitrogen atom or oxygen atom; OCOR″ radicals, in which R″ ischosen from hydrogen atoms and saturated and unsaturated, linear andbranched, hydrocarbonaceous radicals having from 1 to 20 carbon atomswhich are optionally substituted by at least one halogen atom, nitrogenatom, or oxygen atom; and radicals comprising at least one silicon atom;or R¹ and R³ radicals together form a ring having the formula (CH₂)_(n′)which can be substituted by at least one halogen atom, oxygen atom,nitrogen atom, or an alkyl radical having from 1 to 6 carbon atoms, inwhich n′ is an integer ranging from 3 to
 12. 15. A polymer according toclaim 14, wherein at least one of R₁, R₂, R₃, and R₄, each independentlyof one another, is chosen from linear and branched alkyl radicals havingfrom 1 to 6 carbon atoms which are optionally substituted by at leastone halogen atom or at least one —OH radical.
 16. A polymer according toclaim 14, wherein at least one of R₁, R₂, R₃, and R₄, each independentlyof one another, is chosen from linear and branched alkyl radicals havingfrom 1 to 4 carbon atoms which are optionally substituted by at leastone halogen atom or at least one —OH radical.
 17. A polymer according toclaim 14, wherein at least one of R₁, R₂, R₃, and R₁, each independentlyof one another, is chosen from linear and branched alkenyl and alkynylradicals having from 2 to 6 carbon atoms which are optionallysubstituted by at least one halogen atom.
 18. A polymer according toclaim 14, wherein at least one of R₁, R₂, R₃, and R₄, each independentlyof one another, are chosen from linear and branched alkenyl and alkynylradicals having from 2 to 4 carbon atoms which are optionallysubstituted by at least one halogen atom.
 19. A polymer according toclaim 14, wherein at least one of R₁, R₂, R₃, and R₄, independently ofone another, is chosen from C(═Y)R⁵, C(═Y)NR⁶R⁷, YC(═Y)R⁵, cyclicNC(═Y)R⁵, P(═Y)R⁵ ₂, YPR⁵ ₂, and YP(═Y)R⁵ ₂, in which Y is O.
 20. Apolymer according to claim 14, wherein at least one of R₁, R₂, R₃, andR₄, independently of one another, is chosen from C(═Y)NR⁶R⁷, in which R⁶and R⁷ together form an alkylene group having from 2 to 5 carbon atoms.21. A polymer according to claim 14, wherein at least one of R₁, R₂, R₃,and R₄, independently of one another, is chosen from COOR radicals, inwhich R is chosen from linear and branched alkyl radicals having from 1to 6 carbon atoms which are optionally substituted by at least onehalogen atom.
 22. A polymer according to claim 14, wherein at least oneof R₁, R₂, R₃, and R₄, independently of one another, is chosen fromCONHR′ radicals, in which R′ is chosen from hydrogen atoms, saturatedand unsaturated, linear and branched, hydrocarbonaceous radicals havingfrom 1 to 6 carbon atoms which are optionally substituted by at leastone halogen atom, nitrogen atom or oxygen atom.
 23. A polymer accordingto claim 14, wherein at least one of R₁, R₂, R₃, and R₄, independentlyof one another, is chosen from radicals containing at least one siliconatom, wherein said radicals are chosen from —R-siloxane radicals,—CONHR-siloxane radicals, —COOR-siloxane radicals, and —OCO—R-siloxaneradicals, in which R is chosen from linear and branched alkyl,alkylthio, alkoxy, aryloxy, and heterocycloxy radicals having from 1 to20 carbon atoms.
 24. A polymer according to claim 1, wherein saidpolymerized monomeric unit Mk is chosen from: acrylic or methacrylicesters obtained from linear, branched, or cyclic aliphatic alcoholsand/or from aromatic alcohols; C₁-C₄ hydroxyalkyl (meth)acrylates;ethylene glycol, diethylene glycol, and polyethylene glycol(meth)acrylates with a hydroxyl or ether end; vinyl, allyl, methallylesters obtained from linear or branched C₁-C₁₀ aliphatic alcohols,cyclic C₁-C₆ aliphatic alcohols, and aromatic alcohols;N-vinylpyrrolidone; vinylcaprolactam; vinyl-N-alkylpyrroles having from1 to 6 carbon atoms; vinyloxazoles; vinylthiazoles; vinylpyrimidines;vinylimidazoles; and vinyl ketones; (meth)acrylamides obtained fromlinear, branched, or cyclic aliphatic amines or from aromatic amines;(meth)acrylamides chosen from acrylamide, methacrylamide anddi(C₁-C₄)alkyl(meth)acrylamides; olefins; fluorinated or perfluorinatedacrylic and vinyl monomers; monomers containing an amine functionalgroup in the free or else partially or completely neutralized or elsepartially or completely quaternized form; carboxybetaines andsulphobetaines obtained by partial or complete quaternization ofmonomers containing at least one ethylenic unsaturation which containsan amine functional group, wherein said quaternization occurs by asodium salt of a carboxylic acid which contains a mobile halide or by acyclic sulphone; and silicone-containing (meth)acrylates and(meth)acrylamides.
 25. A polymer according to claim 24, wherein saidacrylic or methacrylic esters obtained from linear, branched, or cyclicaliphatic alcohols and/or from aromatic alcohols are obtained fromC₁-C₂₀ alcohols.
 26. A polymer according to claim 25, wherein saidacrylic or methacrylic esters are chosen from methyl (meth)acrylates,ethyl (meth)acrylates, propyl (meth)acrylates, butyl (meth)acrylates,isobutyl (meth)acrylates, and tert-butyl (meth)acrylates.
 27. A polymeraccording to claim 24, wherein said C₁-C₄ hydroxyalkyl (meth)acrylatesare chosen from 2-hydroxyethyl (meth)acrylates and 2-hydroxypropyl(meth)acrylates.
 28. A polymer according to claim 24, wherein saidvinyl, allyl, and methallyl esters obtained from linear or branchedC₁-C₁₀ aliphatic alcohols, cyclic C₁-C₆ aliphatic alcohols, and aromaticalcohols are obtained C₁-C₆ alcohols.
 29. A polymer according to claim28, wherein said vinyl, allyl, and methallyl esters are chosen fromvinyl acetate, vinyl propionate, vinyl benzoate, and vinyltert-butylbenzoate.
 30. A polymer according to claim 24, wherein said(meth)acrylamides obtained from linear, branched, or cyclic aliphaticamines or from aromatic amines are obtained from C₁-C₂₀ amines.
 31. Apolymer according to claim 30, wherein said (meth)acrylamides are chosenfrom tert-butylacrylamide.
 32. A polymer according to claim 24, whereinsaid olefins are chosen from ethylene, propylene, styrene, andsubstituted styrene.
 33. A polymer according to claim 24, wherein saidfluorinated or perfluorinated acrylic and vinyl monomers are chosen from(meth)acrylic esters containing at least one perfluoroalkyl unit.
 34. Apolymer according to claim 24, wherein said monomers containing an aminefunctional group in the free or else partially or completely neutralizedor else partially or completely quaternized form are chosen fromdimethylaminoethyl (meth)acrylate, dimethylaminoethylmethacrylamide,vinylamine, vinylpyridine, and diallylmethylammonium chloride.
 35. Apolymer according to claim 24, wherein said carboxybetaines andsulphobetaines obtained by partial or complete quaternization ofmonomers containing at least one ethylenic unsaturation which containsan amine functional group by a sodium salt of a carboxylic acid whichcontains a mobile halide or by a cyclic sulphone.
 36. A polymeraccording to claim 35, further wherein said sodium salt of thecarboxylic acid is sodium chloroacetate.
 37. A polymer according toclaim 35, further wherein said cyclic sulphone is propane sulphone. 38.A polymer according to claim 24, wherein said silicone-containing(meth)acrylates and (meth)acrylamides are chosen from (meth)acrylicesters containing at least one siloxane unit.
 39. A polymer according toclaim 1, wherein said polymerized monomeric unit Mk is chosen from:(meth)acrylic esters obtained from linear or branched aliphaticalcohols; C₁-C₂₀ (meth)acrylic esters containing at least oneperfluoroalkyl unit; C₁-C₂₀ (meth)acrylic esters containing at least onesiloxane unit; (meth)acrylamides obtained from linear, branched, orcyclic aliphatic amines and/or from aromatic amines; (meth)acrylamideschosen from acrylamides, di(C₁-C₄)alkyl(meth)acrylamides, andmethacrylamides; vinyl, allyl, and methallyl esters obtained from linearor branched C₁-C₁₀ aliphatic alcohols and cyclic C₁-C₆ aliphaticalcohols; vinylcaprolactam; and styrene and substituted styrene.
 40. Apolymer according to claim 39, wherein said (meth)acrylic estersobtained from linear or branched aliphatic alcohols are obtained fromC₁-C₂₀ alcohols.
 41. A polymer according to claim 39, wherein said(meth)acrylamides are obtained from linear, branched, or cyclicaliphatic amines and/or from aromatic amines, and further wherein saidaliphatic and/or aromatic amines are chosen from C₁-C₂₀ amines.
 42. Apolymer according to claim 39, wherein said (meth)acrylamides are chosenfrom tert-butylacrylamide.
 43. A polymer according to claim 3, whereinsaid polymerized monomeric unit Mj is chosen from radicallypolymerizable compounds containing an ethylenic unsaturation having aformula:

in which: R₁, R₂, R₃, and R₄ are, each independently of one another,chosen from: a hydrogen atom; halogen atoms; linear and branched alkylradicals having from 1 to 20 carbon atoms which are optionallysubstituted by at least one halogen atom or at least one —OH radical;linear and branched alkenyl and alkynyl radicals having from 2 to 10carbon atoms which are optionally substituted by at least one halogenatom; cyclic hydrocarbonaceous radicals having from 3 to 8 carbon atomswhich are optionally substituted by at least one halogen atom, nitrogenatom, sulphur atom, or oxygen atom; radicals chosen from CN, C(═Y)R⁵,C(═Y)NR⁶R⁷, YC(═Y)R⁵, cyclic NC(═Y)R⁵, SOR⁵, SO₂R⁵, OSO₂R⁵, NR⁸SO₂R⁵,PR⁵ ₂, P(═Y)R⁵ ₂, YPR⁵ ₂, YP(═Y)R⁵ ₂, NR⁸ ₂, NR⁸ ₃ ⁺, NR⁸ ₂(aryl)⁺, andNR⁸ ₂(heterocycyl)⁺, in which: Y is chosen from O, S, and NR⁸; R⁵ ischosen from linear and branched alkyl radicals, alkylthio radicals, andalkoxy radicals having from 1 to 20 carbon atoms; an OH radical; OM′radicals in which M′ is chosen from alkali metals; aryloxy radicals; andheterocyclyloxy radical; R⁶ and R⁷, independently of one another, arechosen from a hydrogen atom, linear and branched alkyl radicals havingfrom 1 to 20 carbon atoms; or R⁶ and R⁷ together form an alkylene grouphaving from 2 to 7 carbon atoms; R⁸ is chosen from a hydrogen atom,linear and branched alkyl radicals having from 1 to 20 carbon atoms andan aryl radical; COOR radicals, in which R is chosen from linear andbranched alkyl radicals having from 1 to 20 carbon atoms which areoptionally substituted by at least one halogen atom; CONHR′ radicals, inwhich R′ is chosen from hydrogen atoms and saturated and unsaturated,linear and branched, hydrocarbonaceous radicals having from 1 to 20carbon atoms which are optionally substituted by at least one halogenatom, nitrogen atom or oxygen atom; OCOR″ radicals, in which R″ ischosen from hydrogen atoms and saturated and unsaturated, linear andbranched, hydrocarbonaceous radicals having from 1 to 20 carbon atomswhich are optionally substituted by at least one halogen atom, nitrogenatom, or oxygen atom; and radicals comprising at least one silicon atom;or R¹ and R³ radicals together form a ring having the formula (CH₂)_(n′)which can be substituted by at least one halogen atom, oxygen atom,nitrogen atom, or an alkyl radical having from 1 to 6 carbon atoms, inwhich n′ is an integer ranging from 3 to 12.